Reaction product of aldehydes and poly-(diazinyl hydrazino) derivatives of polycarboxylic acids



- filed August 26, 1942, and assigned to ,tiary-butylphenyl, etc.)

. Patented Jan. 11, 1944 UNITED STATES P TENT- orr es REACTION raonoo'r or Annnnynns Ann POLY-(DIAZINYL mmmzmo) DERIVA-' TIVES or POLYOARBOXYLIC ACIDS Y -Gaetano F. .D.Alelio and James W.Underwood,

' Pittsfield, Mass, assignors toGeneral Electric Company, a corporation 'ofNew York No Drawing. Application October 12, 1942,

a Serial No. 461,768

Claims.

This invention relates to the production ofnew 1 synthetic materials and especially tonew reaction products having particular utility in the plastics andcoating arts. Specifically the invention is concerned with compositions of matter comprising a condensation product .of ingredients com- -prising an aldehyde, including polymeric aldehydes, hydroxyaldehydes and aldehyde-addition products, e, g., formaldehyde, paraformaldehyde,-

dimethylol urea, trimethylol melamine, aldol, glycollic aldehyde, etc., and a, compound corresponding to the. following general formula:

' In the'above formula R represents a member of the class consisting of hydrogen and'monovaradicals, moreparticularly halo-hydrocarbon radicals Y represents a polyacyl radical of a poly j carboxylic acid, more particularly analiphatic oran-aromatic polycarboxylic acid, said polyacyl radical being a member of the class consisting of polyacyl radicals of a polycar-bcxylic acid wherein the acyl. groups are-attached directly to each other, polyacyl radicals of a polycarboxylic acid wherein the acyl groups are attached directly to a hydrocarbon radical, and. polyacyl radicals of a polycarboxylic acid wherein the acyl groups are attached directly to a' halo-hydrocarbon rad ical, and n represents aninteger having a value equal to the valency of the polyacyl radical of Y. Instead of the 1,3-diazinyl or pyrimidyl derivatives represented by' the above formula, corresponding derivatives of the 1,2 or ortho-diazines (pyridazines) or of the 1,4- or para-dityl, allyl, methallyl, ethallyl,- crotyl, etc), in-

cluding cycloaliphatic e. g., cyclopentyl,-cyc1o!- pentenyl, cyclohexyl, cyclohexenyl, cycloheptyl, etc.) aryl (e. g., phenyl, diphenyl or xenyl, naphthyl, anthracyl, etc.).; aliphatic-substituted aryl (e. g., tolyl, xylyl, ethylphenyl, propylphenyl, isopropylphenyl, allylphenyl, 2-butenylphenyl, teraryl-substituted all those groups with one or more of their hydrogen atoms substituted by, for example, a halogen,

-more particularly chlorine, bromine, fluorine or iodine. Specific examples of halogeno-substituted hydrocarbon radicals that R in the above formula may represent are: chloromethyl, chloroethyl, chlorophenyl; dichlorophenyl, ethyl chlorophenyl, chlorocyclohexyl, phenyl chloroethyl,

, bromoethyL'bromopropyl, iodophenyl, fluorophenyl, bromotolyl, etc. Preferably R in FormulaI is hydrogen, in which case the compounds may be represented by the general formula:

' lent hydrocarbon andsubstituted hydrocarbon Illustrative examples ofpolyacyl radicals that Y in Formulas I andII may represent are: aliphatic polyacyl g., oxalyl, m'alonyl, s'uccinyl, glutaryl, adipyl, tricarballylyl, etc.). including unsaturated aliphatic polyacyl (e.-g., maleyl, fumaryl, glutaconyl, itaco'nyl, citraconyl, mesaconyl,-glutinyl, aconityl, muconyl, etc.) and ammatic polyacyl (e. g., phtlialyl, naphthalyl, tri-- iso-' methyl, chlorophthalyl, bromophthalyl, phthalyl, terephthalyl, etc.). Preferably Y is a succinyl or a phthalyl radical, although it also advantageously may be. an oxalyl or a malonyl' radical.

The 'poly-(diazinyl I hydrazino) derivatives of polycarboxylic acids that are used in carrying the present invention into eifect are more 'fullydescribed and are specifically claimed in our parent copending application Serial No. 456,263. As pointed out in this copending application, amethod of preparing the diazine derivatives used in practicing the present invention comprises effecting reaction in the presence of a hydrohalide acceptor, preferably a tertiary base, e. g., a tertiary amine such as a trialkyl or triaryl amine, be-

tween (1) a diazine derivative corresponding to the general formula and (2) an acyl halide corresponding to the general formula YXn', where X represents a' halogen atom, and n, Y and R have the same meanings as given above with reference to Formula I, each phatic (e. g., benzyl, phenylethyl, cinnainyl, phenylpropyl, etc.) {and their homologues, as well as halogen represented by X being linked directly to a carbon atom of a carbonyl group of the polyacyl radical represented by Y.

Examples of diazine derivatives einbraced by Formula I that may be used in producing our new condensation products are listed below:

Bis [2,6-di-(methylamino) pyrimidyi-4 hydrazinocarbonyll, which also may be named bis-[2,4-di-(methylami'no) p'yrimidyl-B hydrazinocarbonyll or ox'alyl bis [2,6-di- (methylamino) pyrimidyl-4 hydrazide] Bis [2.6-di-(methylamino pyrimidyl-4 hydrazinocarbonyl] Bis [2,6-di-(methylamino pyrimldyl-4 hydrazinocarbonyl] benzenes AlphabetaL-bis-[2,6-di-(ethylamino) 5-xenyl py- Bis [4,6-di-(methylamino) pyrlmidyl-2 hydrazinocarbonyl] Bis-[4,6-di-(methylamino) pyrimidyl-2 hydra= ,zinocarbonyl] methane Bis (2,6-diamino pyrimidyl-4 hydrazinocarbonyl) Bis (4,6-diamino pyrimidyl-2 hydrazinocarbonyl) methane Alpha,beta,gamma tri-[2,6 di-(methylamino) pyrimidyl-4 hydrazinocarbonyll propane Bis- (4,6-diamino pyrimidyl-2 hydrazinocarbonyl) benrenes Bis (2,6-diamino pyrimidyi-4 hydrazinocarbonyl) benzenes A1pha,beta-bis-(4,6-dlamino pyrimidyl-2 hydrazinocarbonyl) ethane A1pha,beta-bis-(2,6-diamino zinocarbonyl) ethane Bis [2,6-di-(chloromethylamino) 5-ethy1 pyrimidyl-4 hydrazinocarbonyll Bis-[4,6-di-(bromoanilino) pyrimidyl-Z' hydrazinocarbonyl] methane Alphabets, bis-[fi -di-(methylamino) pyrimidyl-2 hydrazinocarbonyl] ethane Alphabeta, bis iifi-di-(ethylamino) pyrimidyi-Z hydrazinocarbonyl] ethane remium-4 hydra- Alpha,beta-bis-[4,6-di-(propenylamino) pyrimidyl-2 hydrazinocarbonyl] ethane Alphabeta bis-[4,6-di-(cyclohexylamino) pyrimidyl-2 hydrazinocarbonyl] ethane A1pha,beta-bis (2,6-dianilino pyrimidyl-4 hydrazinocarbonyl) ethane Bis [2,6-di-(allylamino) S-phenyl -pyrimidyl-4 hydrazinocarbonyll methane Alphabeta bis [2,6-di-(fluoroanilino) pyrimidyl-4 hydrazinocarbonyll ethane Alphabeta his (2,6-dit01uido pyrimidyihydrazinoearbonyi) ethane -Bis-(4,6- dianilino 5-phenyl' pyrimidyl-2 hydra! zinocarbonyl) benzenes Bis (4,6 diamino pyrimidyl-2 ,hydrazinocarbonyl) toluenes I v Bis (4,6 diamino py'rimidyl-2 hydrazinocarbonyl) .xylenes Bis (4,6 'diamino pyrimidyl-2 hydrazinocar- Y bonyl) naphthalenes Bis [4,6 di-(iodoanilino) pyrimidyl-2 hydrazinocarbonyl] benzenes rimidyl-4 hydrazinocarbonyl] ethane Bis-[4,6-di-(bromotoluido) pyrimidy1-2 hydra-' zinocarbonyl] methane 1 Alpha,omega bis-(2-cyclohexylamino 5-chloro-' ethyl 6 anilino pyrimidyl bonyl) phe'nylbutane A1pha,beta,gamma-tri- (4,6-diamino pyrimidyl-2 hydrazinocarbonyl) propane 1,3,5-tri-(4,6'- diamino pyrimidyl-2' hydrazinecarbonyDbenzenes 1 Bis (4,6 diarnino pyrimidyl-Z hydra'zinocarbonyl) chlorobenzenes- Bis- [4,6-di- (cyclohexylamino) 5-cyc1ohexyl pyrimidyl-2 hydrazinocarbonyl] ethanes Bis [2,6-di-(octylarnino) pyrimldyl-4 hydrazinocarbonyl] propanes Bis [4,6-di-(fluoroanilino) pyrimidyl-Z hydra zinocarbonyl] butanes Bis [2,6-di-(iodotoluido) lfi-xenyl pyrimidyl-4 hydrazinocarbonyl] isopentanes Bis-[4,6-di-(bromoanilino) pyrimidyl-Z hydrazinocarbonyl] heptanes Bis- (2,6 diamino pyrimidyl-ihydrazinocarbonyl) chloropropanes Bis- [2,6-di- (chlorotoluido) pyrimidyl-4 hydra-v lzinocarbonyl] benzenes Bis- [4,6-di-(cyclohexenylamino) .5-all'yl pyrimidyl-2 hydrazinocarbonyl'] naphthalenes' Bis-[2,6-di-(pentylamino) 5-methy1pyrimidyl-4 hydrazinooarbonyl] chloronaphthalenes Bis [4,6-cli-(xenylamino)- pyrimidyl-2 hydrazinocarbonyl] xylenes Bis [2,6-di-(naphthylamino) pyrimidyl- 4 hydrazinocarbonyl] ethylbenzenes Bis-[4,6-di-(chloroethylamino) 5-tolyl pyrimidyl-2 hydrazinocarbonyl] toluenes Bis-[2,6-di- (butylamino 5 -butyl pyrimidyl-4 hydrazinocarbonyl] propanes Bis-[4,6-di-(bromopropylamino) 5-octyl pyrim- Alpha,beta bis-(2,6-dixylidino, pyrimidyl-4 hyzinocarbonyll benzenes (-i-anilino 6-methylamino py-..

- tivee employed in D idyl-2 hydrazinocarbonyll butanes It will be pounds embraced by Formula I there are in- .cluded both poly-(diamino pyrimidyi drazinocarbonyD-substituted aliphatic hydrocarbons, more particularly bis-(diamino -py-.

rimidyl hydrazinocarbonyl) alkanes and alkenes,

and poly-(diamino pyrimidyl hydrazinocar-.--

bonyl)-substituted aromatic hydrocarbons.

The present invention is based on our discovery that new particular utility in the plastics and coating arts can be produced by effecting reactionbetween ingredients comprising essentlally an aldehyde, including p lymeric 'a .diazine, derivative. 01 the kind; embraced by Formula I, numerous examples of which have been given above and in ourparentcop application Serial No. 456,263.- Due to-the-numeroua reactive ticing. our invention, cured ','resinous aldehyde-reaction products "prepared their "resistance hydrazinocarnoted that in the above list of comand valuable materials having 7 I I aldehydes,. hydroxyaldehydes and aldehyde-addition 'products,.and=

chains positions in the diazin'efderivato water and organic solvents. ,The gloss and general appearance of molded articles made from molding compounds containing these new resins in heat-convertible state also are exceptionally good. Other improved properties, including improved plasticity combined with rapid-curing characteristics and, also, high resistance to heat and abrasion in the cured state, make the products of the present invention suitable for use in.

fields of utility, for instance in electrically insulating applications, for which resinous mateis used in an amount less than the amount of the primary catalyst, advantageously is a ilxed phosphoric, acetic, lactic, acrylic, malonic, etc.,- .10

rials of lesser resistance to heat, water, abrasion and organic solvents would be wholly unsuited. It has been suggested heretofore that resinous materials be prepared by condensing an aliphatic aldehyde containing a chain of. at the most four carbon atoms with compounds of the general formula where' n represents an integer and is at least 2,- X represents a member of the group consisting and are not the equivalent of, diazine derivatives of the kind embraced by Formula III. Aldehyde-reaction products of diazine derivatives embraced by Formula I likewise are 'difierent from, and are not the equivalent of, reaction products of an aldehyde with a diazine derivative of the kind embraced by Formula III.

In practicing our invention the initial condensation reaction may be carried out at normal or at elevated temperatures, at atmospheric, subatmospheric or superatmospheric pressures, and

under neu ral,alkaline or acid conditions. Preferably the eaction between the components is initiated under alkaline conditions.

Any substance yielding an alkaline or an acid aqueous solution may be used in obtaining alkaline or acid conditions for the initial condensation reaction. For example, we may use an alkaline substance such as sodium, potassium or calcium hydroxides, sodium or potassium oarbonates, mono-, dior tri-ami'nes, etc. cases it is desirable to cause the initialcondensation reaction between the components to take place in the presence of a primary condensation catalyst and a secondary condensation catalyst.

' The primary catalystv advantageously is either an aldehyde-non-reactable nitrogen-containing basic tertiary compound, e. g., tertiary amines such as trialkyl (e. g., trimethyl, triethyl, etc.)

amines, triaryl (e, g., triphenyl, 'tritolyl, etc.)

amines, etc., or an aldehyde-reactable nitrogencontaining basic compound, for instance am monia, primary amines (e. g., ethyl amine, propyl In some I boxylic and polycarboxylic acids and poiyamides.

alkali, for instance a carbonate, cyanide or hydroxide of an alkali metal (e. g., sodium, potassium, lithium, etc.). 5

' Illustrative examples of acid condensation catalysts that may be employed are inorganic or,

organic acids such as hydrochloric, sulfuric,

or acid salts such as sodium acid sulfate, monosodium phosphate, monosodium phthalate, etc. Mixtures of acids, of acid salts or of acids and of acid salts may be employed if desired.

, The reaction between the aldehyde, e. g., fo'rzn aldehyde, and the diazine derivative may be carried outin the presence or absence of solvents or diluents,-other natural or synthetic resinousbodies, or while admixed with'other materials that also can react with the aldehydic reactant or with the diazine derivative, e. g., urea (NHaCONHa), thiourea. selenourea, iminourea (guanidine') substituted ureas, thioureas, seleno- 'ureas and iminoureas; e. g.,'aldehyde-reactab1e urea derivatives such as mentioned in .DAlelio Patent No. 2,285,418, issued June 9, 1942, page 1, column 1, lines 40-49; monoamides of monocarof polycarboxylic acids, e. g., acetamide, halogenated acetamides (e. g., a chlorinated acetamide), 'maleic monoamide, malonic monoamide, phthalic monoamide, maleic diamide, fumaric diamide, malonic dlamide, itaconic diamidasuccinic dlamide, phtha1icdiamide, the monoamide. diamide and triamideof tricarballylic acid, etc; aldehyde-reactable diazines other than the diazine derivatives constituting the primary-components of the resins of the present invention,

e. g., 2,4,6triami nopyrimidine, etc..;" aminotriazines, e. g., melamine, ammeline, ammelide, melem, melam, .melon, numerous other examples being given in various copending applications of one or both of us, for instance 'in DAlelio CO- pending application Serial No. 377,524QflledFebruary--5, 1941, and in applications referred to in said copending application; phenol andsubsti-' tuted phenols, e. g., the cresols, the xylenols, the

tertiary-alkyl phenols and other phenols such as mentioned, for-example, in DAlelio Patent No. 2,239,441, issued April-22, 1941; -monohydric and polyhydrlc alcohols, e. g., b'utyl alcohol, amyl alcohol, heptyl alcohol, octyl alcohol, 2.-'et hylbutyl alcohol, ethylene glycol, propylene glycol, gly'c erine, polyvinyl alcohol, etc.; amines, includin aromatic amines, e g., aniline, etc.; and the like.-

The modifying reactants may be incorporated with the diazine derivativeand the aldehyde to form an intercondensation product by mixing all the reactants and effecting condensation therebetween or by various permutations of reactants as described. for example, in DAlelio Patent No. 2,281,559, issued May 5, 1942 (page 2, column 1, lines 4969) with particular reference to reac-' tions involving a non-haloacylated urea, a halogenated acylated urea and an aliphatic aldehyde.

For instance, we may form a partial condensation product-of ingredients comprising 1) urea or melamine or urea and melamine, (2 a diazine amine, etc.) and secondary amines (e. g2, .di-

propyl amine, dibutyl amine, etc.)'. The secondary condensation catalyst, which ordinarily derivative of the kind embraced by Formula I,

.for example bis-(4,6-diainino pyrimidyl-2 hy-" drazinocarbonyl) bis-(2,6-diamino jpyrimidy1-4 hydrazinocarbonyl), bis [2,6-di-(methylamino) pyrimidyl-4 hydrazinocarbonyl], a poly-(diamino pyrimidyl hydrazinocarbonyl)-substituted aliphatic hydrocarbon, more particularly a bis-(diamino pyrimidyl hydra-zinocarbonyl) alkane amine, etc.

alpha,beta-bis-(2,6-amino pyrimidyl-4- hydrazinocarbonyl) ethane, etc., a poly-(diamino pyrimidyl hydrazinocarbonyl) -substituted aromatic hydrocarbon, e. 3., 9. bis- (4,6-diaminopyrlmidyl;-2 hydrazinocarbonyl) benzene, abis-(2,6-diamirio pyrimidyl-4 hydrazinocarbonyl) benzene, etc.,

and (3) an aldehyde. including polymeric aldehydes, hydroxyaldehydes and aldehyde-addition such, for instance, as alpha,betai-bis-(4,6-di-- amino pyrimidyl-2 hydrazinocarbonyl) ethane,

products, for instance formaldehyde, para-form aldehyde, glyceraldehyde, dimethylol urea, a

polymethylol' melamine, e. 8., hexamethylol mel- Thereafter we may effect reaction between this partial condensation product and, for example, a curing reactant, specifically a chlorinatedacetaxhide, to obtain a heat-curable composition.

Some of the condensation products of this invention are thermoplastic materials even at an thermosetting or potentially thermosetting bodies that convert under heat or under heat and pressure to an insoluble, infuslble state. The thermoplastic condensation products are of particular value as plasticizers for other synthetic resins.v

The thermosetting or potentially thermosetting resinous condensation products, alone or mixed with fillers, pigments, dyes, lubricants, plasticizers, curing agents, etc., may be used, for example, in the roduction of molding compositions.

The liquid intermediate condensation products of the invention may be concentrated or diluted further by the removal or addition of volatile solvents to form liquid coating compositions 02 adjusted viscosity and concentration. The heatto provide a -material that could be molded satisfactorily. 'A sample or the dried and ground molding composition was molded for 3 minutes at 135 C. under a pressure of '2,000 pounds per square inch. The molded piece waswell cured throughout, had excellent water resistance and marked resistance to blisterin when placed in contact with a metal plate heat- ,ed to a temperature of the order of 150 to 175 C. The molding compound showed good plastic flow during molding.

Instead of using chloroacetamide in accelerating the curing of the potentially reactive resinous material, heat-convertiblecompositions may be produced by adding to the partial condensationproduct (in syrupy or other form) direct or active curing catalysts (e. g., citric acid, phthalic anhydride, malonic acid, oxalic acid, etc), or

-. latent curing catalysts (e. g., sodium chloroaceadvanced stage of condensation, while others are convertible or potentially heat-convertible resinous condensation products may be used in liquid state, for instance as surface-coating materials, in the production of paints, varnishes, lacquers, enamels, etc., for general adhesive applications, in producing laminated plywood and other laminated articles,' and for numerous other purposes. The liquid heat-hardenable or potentially heathardenable condensation products may be used directly as casting resins, while those which are of a gel-like nature in partially condensed state may be dried and granulated-to form clear, unfilled heat-convertible resins.

In order thatithose skilled in the art better may. understand how the present invention may be carried into effect, the following examples are given by way of illustration and not by way of limitation. All parts are by weight.

' Example 1 Parts Bis [2,6 di (methylamlno) pyrimidyl-4 hydrazinocarbonyll methane.. 30.3 Aqueous formaldehyde (approx. 37.1% HCHO) 24.3 Sodium hydroximm 1.5'parts water 0.03 Chloroacetamide (monochloroacetamide)- 0.3

All of the above ingredients with the exception of the chloroacetamide were heated together under reflux at the boiling temperature of the mass for 15 minutes. The chloroacetamide was now added and heating under reflux was continued for an additional 3 minutes. The resulting reeinous syrup, which had a pH of 6.6, was mixed with 18.2 parts of alpha cellulose inflock-form and 0.2 part of a mold lubricant, specifically zinc stearateto form a molding (moldable) compos tion. The wet molding compound was dried'at 1 C. until sufllcient moisture had been removed examples are given in various copending applications of one or both of use, for instance in DAlelio copending applications Serial No. 346,962, filed July 23,1940, now Patent No. 2,325,375, and Serial No. 354,395, flied Angust 27, 1940, now Patent No. 2,325,376, both of which applications issued on July 27,1943, and are assigned to the same assignee as the present invention.

Example 2 Parts Bis [2,6 di (methylamino) pyrimidyl-4 hydrazinocarbonyll methane 12.1 Urea 7.2 Aqueous formaldehyde (approx. 37.1%

HCHO) 48.6 Sodium hydroxide in 1.5 parts water 0.03 'Chloroacetamide 0.3

, All 01' the above ingredient with the exception of the choloroacetamide were heated to ether under reflux at boiling temperature for 15 minutes. The chloroacetamide was added at the end of this reaction period and heating under reflux at boiling temperature was continued until a gel had formed in the reaction vessel. This gel was dried at 60 C. until 'suflicient moisture had been removed'to provide a material that could be molded satisfactorily. A sample of the dried and round resin was molded for 3 minutes at C. under a pressure of 2,000 pounds per square inch. The unfilled molded piece exhibited excellent cure and cohesive properties and showed marked resistance to water and heat. The plasticity or the thermosetting resin during molding was very good. Example 3 Parts Bis-[2,6 d1 (methylaminol pyrimidyl 4 hydrazinocarbonyll methane 30.3 Para-amino benzene sulionamide 12.9 Aqueous formaldehyde (approx. 37.1%

HCHO) 48.6 Sodium hydroxide in 2 parts water 0.04

Chloroacetamide 0.4

All of the above components with the exception of the choloroacetamide were heated togeth er under'reflux at boiling temperature for- 15 minutes, after which the above-stated amount ofchloroacetamide was added and refluxing was continued for an additional- 2 minutes. The resinous syrup produced in this manner had a pH of 9.61. It was mixed with30.7 parts alpha cellulose and 0.2 part zinc stearate to form a molding compound. The wet molding composition, was

' dried at 60 c. as described under Example 1. A

well-cured molded piece having excellent cohesive characteristics and marked resistance to heat and water was obtained by molding a sample of the dried and ground molding compound for 3 minutes at 135 C. under ,a pressure of 2,000 pounds per square inch. The molding composition showed satisfactory plastic flow during molding.

Example 4 I Parts Bis [2,6 di (methylamino) pyrimldyl-4 All of the above ingredients with the exception of the chlqroacetamide were heated together under reflux at the boiling temperature of the mass for 20 minutes. At the end of this reaction period the above-stated amount of chloroacetamidewas added and refluxing was continued for an additional 3 minutes. The resulting resinous syrup, which had a pH of. 7.77, was mixed with 23.7 parts alpha cellulose and 0.2 part zinc stearate to form a molding compound. The wet molding composition was dried at 60 C. as described under Example 1. A sample of. the dried and ground molding compound was molded for 3 minutes at 135 C.. under a pressure of 2,000 pounds per square inch. The molded piece was well cured throughout and had a well-knit and homogeneous structure. It also had very good heat resistance. Good fiow characteristicsof the molding compound during molding we're indicated by the amount of flash on the molded piece.

The dimethylol urea in the above formula may be replaced in whole or in part by an equivalent Example 6 z -Bis-[2,6-di-(methylamino) pyrimidyl-4.hy-

drazinocarbonyllmethane 30.3 Bptyl alcohol 27,9 Aqueous formaldehyde (approx. 37.1%

HCHO) 24.3

were heated together under reflux at the boiling temperature of the mass for 16 minutes, yielding a clear, resinous syrup which thereafter was dehydrated by heating it on a steam plate. The

I dehydrated syrup was soluble methylene glycol but was insoluble in water, ethyl alcohol, benzene and Solvatone. When a sample of the dehydrated syrup was heated on a 140 C. hot plate, it cured slowly to an insoluble and infusible state in the absence of a curing agent. More rapidly curing syrups are produced by incorporating, either into the initial syrupy condensationproduct or into the dehydrated syrup, monochloroacetamide, trichloroacetamide, sodium chloroacetate', ethanolamine hydrochlorides, glycine, citric acid. sulfamic acid or other curing agent such as mentioned under Example 1. The resinous material of this example may be employed in the preparation of various coating and impregnating compositions. It may be used as a modifier of var.- nishes of the aminoplast and alkyd-resin types.

Example 7 I Parts Bis- [2,6-di- (metlwlamino) pyrimidyl 4 hydrazinocarbonyll methane 30.3 Acetamide 4.4 Aqueous formaldehyde (approx. 37.1%

HCHO) 48.6 Sodium hydroxide in 2 parts water 0.04

were heated together under reflux at the boiling corporated into samples of the syrup, the individual sample cured to an insoluble and infusible state upon heating on a 140 0. hot plate. In-

' stead of the curing agents just named. other curamount of other aldehyde-addition products, for Y instance by a methylol aminotriazine, e. g., trimethylol melamine, hexamethylol melamine, etc.

Example 5 p Parts Bis-[2,6-di-(methylamino) pyrimidyl-4 hydrazinocarbonyl] methane 30.3 Acrolein 16.3 Sodium hydroxide in 1.5 parts water 0.03 Water 100.0

mg agents such as mentioned under Example 1 maybe incorporated into the syrup to facilitate its conversion under heat to an insoluble and infusible state. For example, when a small amount of an acid, specifically hydrochloric acid, was

added to the syrup and the acid-modified syrup then was applied to a glass plate, a hard, transparent, glossy, smooth and highly water-resistant. cured film was formed by baking the coated plate for several hours at C. The resinous material of this example may be used in the preparation of baking varnishes or other coating and-impregnating compositions. It also may be used as a modifier of other aminoplasts and compatible synthetic resins.-

Ezca'mplet Parts Bis-[2,6-di-(methy1aminor pyrimidyl 4 hydrazinocarbonyll methane 30.3 Diethyl malonate 12.0 Aqueous formaldehyde (approx. H 37.1% HCHO) L 48.6 Sodium hydroxide in 2 parts water. 0.04

were heated .together under reflux at the boiling temperature of the mass for 15 minutes, yielding a resinous syrup having curing characteristics much the same as the syrupy condensation prod- I inous syrup was heated on not of Example 7. The dehydrated syrup was soluble in water, ethyl alcohol and ethylene glycol butwas insoluble in benzene and Solvatone. A- sample of the dehydrated syrup was acidified with a small amount of hydrochloric acidlafter which a glass plate was coated with a sample of the acidified syrup. The coated plate was baked for several hoursat 60 C. The baked film was hard,

transparent, sm 'th and water-resistant. The

resinous material f this example may be used in the preparation of coating and impregnating compositions, in the production of molding compounds, as a modifier of other synthetic resins,

as a laminating varnish and for numerous other purposes.

Example 9 Parts All of the above ingredients with the exception of the chloroacetamide were heated together unmg gig g gg g fggg g 4 hy 30 3 I der reflux at the boiling temperature of the mass Gjyppfinp y 20 for 16 minutes, at the end of which period-of time the chloroacetamide was added and heating gg gg formaldehyde 371% 48 6 under reflux at boiling temperature was consodium hydro x1 de in 2 parts water 0.04 tinued for an additional minutes. The resultwere heated together under reflux at the boilin temperature of the mass for 15 minutes. The resulting resinous syrup was potentially heat-curable as shown by the face that when phenacyl chloride, chloroacetamide, sodium chloroacetate or other curing agent such as mentioned under Example 1 was incorporated into the syrupy condensationproduct, followed by heating on a 140 C. hot late, the syrup cured rapidly to an i n- A glass plate was 3 soluble and infusible state. coated with a sample of the dehydrated syrup into which had been incorporated a small amount of a curing agent, specifically hydrochloric acid. The coated plate was baked for several hours at 60 C. A hard, flexible, transparent, glossy, smooth and very water-resistant, baked film was formed on the plate. The resinous material of this example is especially suitable for use in the preparation of baking varnishes andother coating and impregnating compositions.

Example 10 A liquid, phenol-formaldehyde partial condensation product was preparedby heating together a mixture of the following components for 4 hours at 65 0.:

Parts Synthetic phenol--. 90.0 Aqueous formaldehyde (approx. 37.1%

HCHO) 195.0 Potassium carbonate 2.85

These ingredients were heated together under reflux at the boiling temperature of the mass for 40 minutes. when a sample of the resulting resa 140 C. hot plate, it cured slowly to an infusible 'mass in the absence of a curing agent. The addition of phthalic acid, citric acid, oxalic acid or other acidic material to asaaoer the syrupy condensation product accelerated its conversion to an insoluble and infusible state under heat. The resinous material of this'example may be used in the production of molding compounds or it may be employed in the preparation of .various coatingand impregnating compositions.

Example 11 Parts l0 Bis-[2,6-di-(methy1amino) pyrimidyl-yi hydrazinocarbonyl] 39.0

Aqueous formaldehyde (approx. 37.1% HCHO) .32.4 Sodium hydroxide in 1.7 parts water 0.035 15 Chloroacetamide 0.35

mg resinous syrup was mixed with 20.5 parts 'alpha cellulose and 0.2.part zinc stearate to form amolding compound. The wet molding composition was dried at room temperature until sumcient moisture had been removed to provide a material that could be molded satisfactorily. A sample of the dried and ground molding compound was molded for 3 minutes at 135 C. under a pressure of 2,000 pounds per square inch. The molded piece was well cured throughout and had a well-knit and homogeneous structure. It had 5 very good water resistance as evidenced by the fact that it absorbed only 2.3% by weight of water when immersed in boiling water for 15 minutes, followed by immersion in cold water for 5 40 minutes. (When similarly tested for water resistance, molded articles made from molding compounds containing the ordinary urea-formaldehyde resins usually absorb about 5 to 7% by weight ofwater.) Satisfactory plastic flow of cated by the amount of flash on the molded piece.

' Eatample 12 I I Parts Bis-[2,6-di-(methylamino) pyrimidyl 4 hydrazinocarbonyl] -L 11.7 Urea l Y 7.2 Aqueous formaldehyde (approx. 37.1%.

HCHO) 1 48.6 s5 Sodium hydroxide in 1.7 parts water 0035 Chloroacetamide All of the above ingredients with the exception of the chloroacetamide were heated together un- -der reflux at boiling temperature for 10 minutes, after which the chloroacetamide was added and refluxing was continued for an additional 5 minutes. A molding compound was prepared from the resulting resinous syrup, which had a pH oi 7.95, by mixing therewith 19.8 parts alpha cellulose and 0.2 part zinc stearate. The wet molding composition was dried as described under Example 11. An excellently cured molded piece having good water resistance and good cohesive characteristics was produced by moldings. sam ple of the dried and ground molding compound for 3 minutes at C. under a pressure of 2,000 pounds per square inch. The plasticity of the molding compound during molding was satisfacthe molding compound during molding was indi- 2,839,061 Example 13 Example 15 Parts Parts Bis- [2,6-di-(methylamlno) pyrimldyl-4 hy-' Bis-[2,6-di-(methylamino) pyrimidyl-4 hydrazinocarbonyl] 39.0 drazinocarbonyll 29.3 5 Acr l 22.4 Para-amino benzene sulfonamide .i 12.9 Aqueous ammonia (approx. 28% NI-Ia) 3.9 Aqueous formaldehyde (approx. 37.1% Sodium hydroxide in 1.5 parts water 0.03

HCHO) 48.6 Water 20.0 sodium hydroxide in 9 Water were mixed together, theacrolein being added Chloroacetamide last. An exothermic reaction tookplace immediately upon the addition of the acrolein and aresinous mass precipitated from the solution. A resimms Syrup was Prepared by heating This resin cured to an insoluble and infusible gether all of the above components with the exstate m the absence of a'curing agent when a oeption of the chloroacetamide for 7 minutes at l Small sample of It was heatedv on a n boiling temperature under reflux, after which plate. The'resinous material of this example the chloroacetamide was added and heating under may be used in the preparation of molding reflux at boiling temperature was continued for poumm an additional 3 minutes. 'A molding compound Efpample 1 was produced by compounding this syrup, which v Parts, had a pH of 10.05, with 27 parts alpha cellulose Bis [2,6 di (methy1am1no) pyrim1dy] 4 h and 0.2 part zinc stearate. The wet moldingdrazjnocarbonyl] 39,0 composition was dried and molded as described Butyl 1 1 1 37,0 under Example 11. The molded article was Well Aqueous formaldehyde (approx, 37- 1% cured throughout, had a well-knit and homo- 2 HCHO) 32,4 geneous structure, exceptionally good water re-' sodium hydroxide in parts at 0115' Slam-me and mgh degree of resiliency The were heated together under reflux at the boiling plasticity of the molding compound during moldtemperature of the mass for 15 minutes. The mg was very good. The molding composition of this example would be especially suitable for use 30 resum-ng resinous syrup was dehydrgtled by heat in the production of screw caps and other molded mg it on steam plate The dehydrated. Syrup Q articles that are to be ejected hot from the mold was-soluble m ethylene glycol but was insomble' or substantially so, in water, ethyl alcohol, benzene and Solvatone. When chloroacetamide, sul- Ewample 14 famic acid or other curing agent such as men- --ti0ned under Example 1 was added to the initial Parts syrupy condensation product or to the dehy- Bis-[2,6 -di- (methylamino) pyrimidyl-i drated syrup, followed by'heating on a 140 C. hydrazinocarbonyl'l 29.3. hot plate, the material cured to an insoluble and Dimethylol urea (commercial grade, con- 40 infusible state. The product of. this example taining approx. 11% by weight of may be used in the preparation of various liquid water) 40.4 coating and impregnating compositions; Sodium hydroxide in 1.5 parts wate 0.03 Chloroacetamide 0.3 Parts m" 5 Bis-I2,6-di-'(methylamino) pyrimidyl-4 hy.- s drazinocarbon'yll 39.0 1 All of the above ingredients with the exception Acetamides of the chloroacetamide were heated together un- Aqueous formaldehyde v(al'iprm- I 371% der reflux at the boiling temperature of-the mass HQHO) for 15 minutes. The chloroacetamide was now .Sodmm hydmxlde 2. partswater 094 added and heating under reflux at boiling temwere heated together under reflux at the boiling perature was continued for an additional 4 mintemperature of the'mass for 15 minutes. The utes. The resulting resinous syrup had a pH of resulting resinous syrup was potentially heat- 8.01.- It was mixedwith 20 parts alpha cellulose curable as shown by the fact that when sulfamic and 0.2 part zinc stearate to form a moldingpoma'cid, chloroacetamide or other curing agent such pound. The wet molding composition was dried asmentioned under Example 1 was incorporated first at room temperature and then at C. therein, followed by heating on 'a 140 C 'hot until sufiicient moisture had been removed to plate, theresin cured to an insoluble and infusiprovide a material that could be molded satis- 60 ble state. factorily. An excellently cured molded piece I Example 18 having good cohesive characteristics, amarked P rt degree of resiliency and good water resistance Bis-[2,6-di-(methylamino) pyrimidyl-4 hy-' was produced by molding a sample of the dried drazinocarbonyl] 39,0 an ground molding compound for 3 minutes at t l ma nate 16:0 135 C. under a pressure of 2,000 pounds per Aq e u f m d hy approx. 37.1% square inc Satisfactory plastic flow durin Q? 3 -4 molding was indicated by the amount of fla h on Sodium hydroxide in 2 parts water; 0.04 the molded piece and by its homogenei y and were heated together under reflux at the boiling. evenness of structure. temperature of the mass for 6 minutes, at the. The dim'ethylol urea in the above formula may end of which reaction period a resinous mass prebe repla in whole 01 in P by an equivalent cipitated from the solution; This resin cu'red'to amount of other aldehyde addifion products, for an insoluble and infusible state in the absence instance by a methylol aminotriazine, e. g., triof a curlngagent when asmall sample of it was methylol melamine, hexamethylol melamine, etc. I j

heated .On a C. hot p1ate.

. plate 8. A A n Example I Parts Bis- [2,6-di-(methylamino) pyrimidyl-4 hydrazinocarbonyl] 39.0 Glycerine 9.2 Aqueous formaldehyde (approx. 37.1%

HCHO) 48.6 Sodium hydroxidein 3'partswater 0.06

were heated together under reflux at the boiling temperature .of the. mass ford? minutes. The resulting resinous. syrup was dehydrated by heating it on a hot plate. The dehydrated syrup bodied to a thermoplastic resin upon being heated further on a 140 C. hot plate. When a small amount of phthalic anhydride or other curing agent such as mentioned under Example 1 was incorporated into the initial syrupy condensation product or into the dehydrated syrup, the

material cured to an infusible resin upon being heated on a 140? C. hot plate. Glass plates were coated with samples of the dehydrated syrup,

one of which contained a small amount of an acid, specifically hydrochloric acid, as a curing agent. The coated plates were baked for several hours at 60 C. In both'cases the baked films were hard, glossy, transparent and wrinkled, and adhered tightly to the glass surface. The hy drochloric acid-modified syrup yielded a baked film that was more water resistant and less wrinkied than the film obtained from the unmodified syrup. I

Example 20 Parts Bis-[2,6-di-(methylamino) pyrimidyl-4 hydrazinocarbonylL. 39.0

Polyvinyl alcohol 4.4 Aqueous formaldehyde (approx. 37.1%

HCHO) 32.4 Sodium hydroxide in 2- parts water 0.04

were heated together under reflux at the boiling temperature of the mass for 15 minutes. When a sample of the resulting resinous syrup was heated on a 140 C. hot plate, itbodied to a thermoplastic resin. However, when a. small amount of an acid, specifically hydrochloric'acid, was incorporated into a sample of the syrupy condensation product, the resulting material was converted into an infusible .mass when the sample was heated ona 140 C.-hot plate. When a glass edfor several hours at 60 C., an adhering, glossy, transparent, thermoplastic film was formed on the plate.. Under the same heat treatment a glass plate that had been coated with a sample of the syrup into which had been incorporated a small amount of hydrochloric acid as a curing agent gave a baked film that was hard, transparent, flexible and glossy. Molding compositions or various liquid coating and impr'egnating compositions may be produced from r the resinous material of this example.

Example 21 g Parts 318- [2,6-di-(methy1'aminoi pyrimidyl-4 hya hydrazinocarbonyll' methane 30.3 Aqueous formaldehyde (approx..37.1%

HCHO) I v 48.6 Sodium hydroxide in 2 parts water 0.04 Polyvinyl alcohol .3.- 3.4-

I were heated together under retlux at the boiling temperature of the mass for 15 minutes. The

mul mresin'o syrup was potentially heatcoated with the unmodified syrup was heatcurable as evidenced by-the fact that when a small amount of -9. curing agent, specifically hydrochloric acid, was incorporated into the syrupy reaction product, followed by heating on a 140 5 0. hot plate, the syrup was converted into an opaque, infusible resin. Glass plates were coated with samplesof the resinous syrup, one of which was modified by the addition of a small amount of hydrochloric acid. The coated plates were baked for several hours at 60 C. The baked films, in both cases, were hard, transparent, glossy, smooth, flexible and water-resistant. The resinous material of this example, either with or without a curing agent such as menproduction of molding compositions or it may be employed in the preparation of various liquid coating and impregnating compositions. If thermosetting molding or coating compositions are desired, a suitable curing agent should be incorporated into the syrupy condensation product or-into the molding or coating composition contaming such condensation product. i

It will be understood, of course, by those skilled in the art that the reaction between the aidehyde and the diazine derivative may be effected at temperatures ranging, for example, from room temperature to the fusion or boiling temperature of the mixed reactants or of solutions of the mixed reactants, the reaction proceeding more slowly at normal temperature than at elevated temperatures in accordance with the general law of chemical reactions. Thus, instead of effecting reaction between the ingredients of the foregoing examples under reflux at the boiling temperature of the mass as mentioned in all but one (Example 15) of the examples, the reaction between the components may be carried out at lower temperatures, for example at temperatures ranging from room temperature to a temperature near the boiling temperature using longer reaction periods and, in some cases, stronger catalysts and higher catalyst concentrations.

It also will be understood by those skilled in the art that our invention is not limited to condensation products obtained by reaction of ingredients comprising an aldehyde and the specific diazine derivative embraced by Formula I that is named in the above illustrative examples. Thus, instead of bis- [2,6-di-(methylamino) pyrimidyl-4 hydrazinocarbonyl] and bis-[2, 6-di- -(methylamino) pyrimidyl-4 hydrazinocarbonyll methane, we may use, for example, bis-[4,6-di-' drazinocarbonyl) methane, other poly-(diamino pyrimidyl hydrazinocarbonyl) -substituted aliphatic hydrocarbons, more particularly bis-(diamino pyrimidyl hydrazinocarbonyl) alkanes such, for example, as aipha,beta-bis-(2,6-dipyrimidyl hydrazinocarbonyl') toluene, etc., or

any other diazine derivative of the kind embraced 1. by Formula I, numerous examples of which tionedunder Example 1, may be used in 'the zinocarbonyl], bis-(2,6-diamino pyrimidyl-4 hy-- have been given herein and in our copending application Serial No. 456,263. I 1 In producing these new condensation products the choice. of the aldehyde is dependent. largely upon economic considerationsland upon the particular properties desiredin-the finished product.- We prefer to use'as the aldehydic reactant formaldehyde or compounds engendering formaldehyde, e. g., paraformaldehyde, hexamethylene tetramine, etc. Illustrative examples of other aldehydes that. may be used are acetaldehyde,

propionaldehyde, butyraldehyde, heptaldehyde, "octaldehyae, methacrolein, crotonaldehyde, benzaldehyde, furfural, hydroxyaldehydes, (e. g.,

aldol, glucose, glycollic' aldehyde, glyceraldehyde,

etc.),- mixtures thereoflor mixtures of formalj monoethyl ether, diethylene g ycol monobutyl ethe'r,-etc.; amides; e. g., formamide, steara-' mide, acrylamide. benzene sulfona'mides, toluene sulfonamides, adipio diamide, phthalamide, etc.;

amines, e. g., ethylene diamine, phenylene diamine, etc.; ketones, including halogenated ketones; nitriles, including halogenated nitriles,

dehyde (or compounds engendering formaldef hyde) with. such aldehydes. Illustrative examples of aldehyde-addition products that may be employed instead of the aldehydes themselves are the monoand poly- (N-carbinol), derivatives of urea, thiourea, selenourea and iminourea, and of substituted ureas, thioureas, selenoureas and iminoureas, mono-- and poly-(N-carbinol) derivativesoi amides of polycarboxylic acids, er g.,

maleic, itaconio, fumaric, adipic, malonic, succinic, citric, phthalic, etc., monoand poly-(N- .carbinol) derivatives of the aminotriazines, of the aminotriazoles, etc. Particularly good results are obtained with active methylene-containing bodiessuch as a methylol urea, more particularly monoand di-methylol ureas, and a methylol aminotriazine, e. g., monomethylol melamine and polvmethylol melamines (di-,

amount correspo'nclinrg to at least one mol of the aldehyde, specifically formaldehyde, for each mol of the diazine derivative. Thus, we may use, forfexample, from 1 to 15 or 20 or more mols of an aldehyde for each molot the diazine derivative. When the aldehyde is available for reaction in the formof an alkylol-derivative, more e. g., acrylonitrile, methacrylonitrile, chloroacetonitriles, etc.; acylated ureas, including halogenated acylated ureas of the kind described, for

example, in DAlelio Patent No. 2,281,559, issued May 5, 1942; and others,

The modifying bodies also may take the form of high molecular weight bodies with or without "resinous characteristic, for example hydrolyzed wood products, formalized cellulose derivatives, lignin, protein-aldehyde condensation products,"

aminotriazine-aldehyde condensation products (e g., melamine-formaldehyde condensation products), aminotriazole -aldehyde condensation products, etc,- Other examples of modify! ing' bodies are the urea-aldehyde condensation products, the aniline-aldehyde condensation products, furfural condensation products, phenol-aldehyde condensation products, modified or unmodified, saturated or unsaturated polyhydric alcohol-polycarboxylic acid condensation products, water-"soluble cellulose derivatives, natural gums and resins. such as shellac, rosin, etc.; polyvinyl compounds such as polyvinyl esters, e. g., polyvinyl acetate, Polyvinyl butyrate, etc., polyvinyl ethers, including polyvinyl acetals, specifically polyvinyl formal, .etc.

Instead of efiecting reaction between a diazine derivative of the kind embraced by Formula I and an aldehyde, specifically formaldehyde, we may cause an aldehyde to condense with a salt (organic or inorganic) of the diazine derivative or with av mixture of the diazine derivative and a salt thereof. Examples of -organic and.inorganic acids that may be used in the-preparation of such salts are hydrochloric; sulfuric, phosphoric, acetic, chloroacetlc, propionic, .butyric,

valeric, acrylic," oxalic, malonic, methacrylic, poly- I in accordance with conventional practice to. proparticularly a methylol derivative such, for instance, as 'dimethylolurea, trimethyl'ol melamine, etc., then higher amountsof such aldehyde-addition products are used, for instance alkylol derivatives'for each mol of the diazine derivative.

As indicated hereinbefore, and as further shown by a number of the examples, the proper-'- ties of the fundamental resins of this invention may be varied widely by introducing other modifying bodies before, during or afterefiectingcondensation between the primary components. Thus, as modifying agents we may use,

Irom 2 or 3 up to 35 or 40 or more mols of such the production of molding for example, mono-hydric alcohols, e. g., methyl,

ethyl, propyl, isopropyl, isobutyl, hexyl, etc., a1- cohols; polyhydric alcohols such, for example, as diethylene glycol, triethylene glycol, pentaerythritol, etc.; alcohol-ethers, e. g., ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethyle'neglycol monomethyl ether, diethylene glycol acrylic, polymethacrylic, succinic, fumaric, benzoic, etc.

Dyes, pigments, plasticizers, curing agents, mold lubricants, ,opacifiers andjvarious fillers (e. g., wood flour. Blass fibers, asbestos, including defibrated asbestos, mineral wool, mica, cloth cuttings, etc.) may be compounded with the resin adir ic, maleic,

vide various thermoplastic and thermosetting molding compositions. The modified and unmodified resinous compo-. sitions of this invention have a wide variety of uses. For example, in addition ,to their use in compositions, they may be employed as modifiers of other natural andsynthetic resins, as laminating varnishes in the production of laminated articles wherein sheet materials, e. g., paper, cloth, sheet asbestos, wood veneer, etc., are coated and impregnated with they resin,

and pressure. They may be atlilicle', for. bonding together abrasive grains, in

such. for instance, .as grindstones, sandpaper's,

etc., in the manufacture of electrical resistors,

etc. They maybe employed for treating cotton,

salicylic, phthalic,.lcamphoric,

superimposed and thereafterv united under heal;

used in the production of wire or baking enam-.-

form a laminated mica' production of resin-bonded abrasive articles linen and other cellulosic materials in sheet or other form. They also may be used as impregnants for electrical coils and for other electrically insulating applications. I

Whatwe claim as new and desire to secure by Letters Patent of the United States is:

1. A composition of matter comprising the product of reaction of ingredients comprising an aldehyde and a compound corresponding to the I general formula where R represents a member or the class consisting of hydrogen and monovalent hydrocarbon and halo-hydrocarbon radicals, Y represents a polyacyl radical of a polycarboxylic acid, said polyacyl radical being a member of the class consisting of polyacyl radicals vof a polycarboxylic agid wherein the acyl groups are attached directly to each other, polyacyl radicals of a polycarboxylic acid wherein the acyl groups are attached directly to a hydrocarbon radical, and polyacyl radicals of a polycarboxylic acid wherein the acyl groups are attached directly to a halo-hydrocarbon radical, and n represents an integer having a value equal to the valency or the polyacyl radical of Y.

2. A composition of matter comprising the product of reaction of ingredients comprising formaldehyde and a compound corresponding to the general formula where R represents amember oi the class consisting of hydrogen and monovalent hydrocarbon and halo-hydrocarbon radicals, Y represents a polyacyl radical of a polycarboxylic acid, said polyacyl radical being a member of the class consisting of polyacyl radicals of a polycarboxylic acid wherein the acyl groups are attached directly to each other, polyacyl radicals of a polycarboxylic acid wherein the acyl groups are attached directly. to -a hydrocarbon radical, and

polyacyl radicals of a polycarboxylic acid wherein the acyl groups are attached directly to a halohydrocarbon radical, and n represents an integer having a value equal to the valency of the polyacyl radical of Y.

3. A composition of matter comprising the product of reaction of ingredients comprising an aldehyde and a compound corresponding to the general formula where Y represents a polyacyl radical 01' an unsubstituted aliphatic polycarboxylic acid and n represents an integer having a value equal to the valency oi the polyacyl radical oi Y.

4. A composition of matter comprising the.

product pireactlon of ingredients comprising an aldehyde anda compound corresponding to the general formula where Y represents a polyacyl radical of an unsubstituted aromatic polycarboxylic acid and n represents an integer having a value equal to the valency of the polyacyl radical of Y.

5. A composition as in claim 1 wherein the reaction product is the product obtained by efiecting initial reaction between the stated components under alkaline conditions. Y

6. A compositionas in claim 1 wherein the reaction product is an alcohol-modified reaction product of the stated components.

'7. A heat-curable resinous composition comprising the heat-convertible condensation product of ingredients comprising formaldehyde and a compound corresponding to the general formula is] C\ where Y represents a polyacyl radical of a polycarboxylic acid, said polyacyl radical being a member of the class consisting of polyacyl radicals of a polycarboxylic acid wherein the acyl groups are attached directly to each other, polyacyl radicals of a polycarboxylic acid wherein the acyl groups are attached directly to a hydrocarbon radical, and polyacyl radicals of a polycarboxylic acid wherein the acyl groups are attached directly to a halo-hydrocarbon radical, and n represents an integer having a value equal to the valency or the polyacyl radical or Y.

8. A product comprising the cured resinous composition of claim 'I.

9. A composition of matter comprising the resinous condensation product of ingredients comprising an aldehyde and a bis-(diamino pyrimidyl hydrazinocarbonyl) alkane.

10. A. composition of matter comprising the resinous condensation product of ingredients comprising an aldehyde and an alpha, beta-bis- (diamino pyrimidyl hydrazinocarbonyl) ethane.

11. A composition of matter comprising the resinous condensation product of ingredients comprising an aldehyde and a bis-[di-(methylamino) pyrimidyl hydrazinocarbonyll.

12. A resinous composition comprising the product of reaction of ingredients comprising formaldehyde and bis-[2,6-di-(methylamino) pyrimidyl-4 hydrazinocarbonyl].

13. A composition of matter comprising the resinous condensation product of ingredients comprising an aldehyde and a bis-(diamino pyrimidyl hydrazinocarbonyl) benzene.

14. A composition comprising the resinous product or reaction of ingredients comprising a urea, an aldehyde and a compound corresponding to the general formula 1 where R represents a member of the class conthe acyl groups are attached directlyto a hydrosisting oi hydrogen and 'monovalent hydrocarbon and halo-hydrocarbon radicals.- Y represents a polyacyl radical oi a polycarboxylic acid, saidpolyacyl radical being a member oi the class consisting oipolyacyl radicals oi a polycarboxylic acid wherein the acyl groups are attached directly to each other. polyacyl radicals oi a polywhere Y represents a poLvacyl radical oi a polycarboxylic acid, said polyacyl radical being a member of the class consisting oi p0lyacy1 radicals oi a polycarboxylic acid wherein the acyl groups are attached directly to each other, polyacyl radicals of a polycarboxylic acid wherein the acyl groups are attached directly to a hydrocarbon radical, and polyacyl radicals oi a poly-' carboxylic acid wherein the acyl groups are attached' directly to a halo-hydrocarbon radical, and n represents an integer'havlng a value equal to the valency oi the polyacyl radical oi Y.

16. A composition comprising the resinous product oi reaction oi ingredients comprising dimethylol urea and a compound corresponding to the general iormula l-( i r i N i N J where Y represents a polyacyl radical oi a polycarboxylic acid, said polyacyl. radical being a member oi the class consisting oi polyacyl radigals oi a polycarboiwlic acid wherein the acyl groups are attached directly to each other, polyacyl radicals di apolycarboxylic acid wherein carbon radical; and polyacyl radicals oi a polycarboxylic acid wherein the acyl groups are attached directly to .a halo-hydrocarbon radical, and n represents an integer having a value equal to the valency oi the polyacyl radical oi Y.

1'7. A composition comprising the resinous product oi reaction oi ingredients comprising an aminotriazine, an aldehyde and a compound corresponding to the general iormula Ha ti m Y i L Y J where It represents a member oiths class consisting oi hydrogen and monovalent' hydrocar- 11 a polyacyl radical oi ap lycarboxylicacid, said mlyacyl radical being amembcr oi the class con.

sisting oi-polyacyl oi a polycarboxylic acid wherein the acyl groups are attached d1:

- rectly to each other, polyacyl radicals oi a polycarboxylic'acid wherein the acyl groups are attached directly 'to a hydrocarbon radical, and

polyacyl radicals'oi a polycarboxylic acid wherein the acyl groups are attached directly to'a halohydrocarbcn radical, and n represents an integer having a value equal to the valency oi the polyacyl radical oi Y. 4

18. A composition comprising the resinous product oi reaction oi ingredients comprising melamine, iormaldehvde and a compound corresponding to the general iormula where Y represents a polyacyl radical oi a polycarboxylic acid, said polyacyl radical. being a member oi the class consisting oi polyacyl radicals oi a polycarboxylic acid wherein the acyl groups are attached directly to each other, polyacyl radicals oi a polycarboxylic acid wherein the acyl groups are attached directly to a hydrocarbon radical, and polyacyl radicals oi a polycarboxylic acid wherein the acyl groups are attached directly to a halo-hydrocarbon radical, and n represents an integer having a value equal to the valency oi the polyacyl radical oi Y.

19. A heat-curable composition comprising the heat-convertible resinous reaction product oi (l) .a partial condensation product oi ingredients wwhere Y represents a polyacyl radical oi a polycarboxylic acid, said polyacylradical being a member oi the class consisting oi polyacyl radicals oi as polyearbonlicacid wherein the acyl groups are attached directly to each other, polyacyl radicals oi a polycarbonlic acid wherein the acyl groups are attached directly to a hydrocarbon radical, and polyacyl radicals oi a polycarboxylic acid wherein the'acyl groups are atbon and halohydrocarbcn radicala'Y r nr m u tached directly to a hais hyd'ccarbon radical, and n represents an integer having a value equal'to the valency oi the polyacyl radical oi Y, and ('2) a curing reactant.

' 20. The method oi preparinegrrnew synthetic compositions which comprises ecting reaction between ingredients comprising an aldehyde and a compound corresponding to the ceneral iormuia a polyacyl radical of a polycarboxylic'acid, said polyacyl radical beinga member of the class consisting 01' polyacyl radicals of a polycarboxylic acid wherein the acyl groups are attached directly to each other, polyacyl radicals 01' a polycarboxylic acid wherein the acyl groups are attached directly to a hydrocarbon radical, and

polyacyl radicals of a polycarboxylic acid wherein the acyl groups are attached directly to a halo-hydrocarbon radical, and n represents an integer having a value equal to the valency of the 5. polyacyl radical of Y GLETANO F. DALELIO. JAMES W. UNDERWOOD.

CERTIFICATE OF CORRECTION. Patent No. 2,559,061. January 11, 192 1,,

GAETANO F. DYALELIO, ET AL.

It is hereby certified thaterror appears in the printed. specificationof the above numbered patent requiring correction as follows: Page 1, sec- 0nd column, line 27-28, for "trimethyl" read -trimes yl-- page 2, first column, line 9, after "(methylamino" insert a closing parenthesis; line l0 after the bracket insert "methane"; page 1+, first column, line 5, for 2,6-amiho" read 2, 6diamin0--; line 6, for "LL,6-diaminopyrimidyl-Zf' read .|l,6-diamino pyr1midyl2-; and second column, line 5A, for "use read --u's--; page 5, first cplumn, line 2, for "choloro'acetamide" read chl'oroacetamide; page 6, first column, line 29, for "face" read --fact-- line 61;, before "m'ethylaminoP' insert an opening parenthesis; page. 9, first column, line 113., after "hydroxyaldehydes" strike out the comma; line 11.7, for "cogrespondinrg" read --corresponding--; line 68, for "mono-hydric read monohydric--; and secondcolumn, line 15, for eharacteristic" read"characteristics"; page 11, second column, line 14.5, for thatportion-pf the formula reading "R-C" read --H-C--; line 68', for"H-C" read -H- C-; and that the said Letters Patent should be read with this correction therein that the same may conform to the record of the case in the Patent Office.

Signed and sealed this 18th day of April, A. D. 1961;.

Leslie Frazer (Seal) 7 Acting Commissioner of Patents. 

